Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
  • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
  • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0209—Impregnation involving a reaction between the support and a fluid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
  • C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
  • B01J2231/12—Olefin polymerisation or copolymerisation
  • B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Definitions

• the present invention discloses the preparation of solid activating systems for the polymerisation of olefins.
• the present invention relates to an activating support for immobilising metallocene or post-metallocene complexes, in order to promote heterogeneous polymerisation of ethylene and alpha-olefins .
• catalysts are however not adapted to heterogeneous polymerisation, such as suspension or gas phase polymerisation. These processes offer many advantages, among others, they allow the preparation of a polymer in granular form having a defined particles size distribution.
• That activating agent however also exhibits disadvantageous features such as superstoechiometric quantities of MAO ranging from MAO:catalyst precursor ratios of 10 2 :1 to 10 4 :1. Consequently, there is a great need to develop new activating agents that can either replace MAO or decrease its necessary quantities, (see for example E. Y.-X. Chen, T.J. Marks, "Cocatalysts for metal-catalyzed polymerization: Activators, Activation processes, and structure-activity relationships" in Chem. Rev., 100, 1391 -1434, 2000).
• Nicholls "Base-free cationic 14-electron titanium and zirconium alkyls: in situ generation, solution structures, and olefin polymerization activity” in Angew. Chem. Int. Engl., 29, 780- 782, 1990 ; X. Yang, CL. Stern, T.J. Marks "Cation-Ike homogeneous olefin polymerization catalysts based upon zirconocene alkyls and tris- (pentafluorophenyl)borane" in J. Am. Chem. So ⁇ , 113, 3623-25, 1991 ; M. Bochmann, S.J.
• Another goal of this invention is the preparation of heterogeneous olefin polymerisation catalytic systems having hardened catalyst grains for use in gas phase or slurry polymerisation processes and then to provide a method for preparing polymers having improved morphology, thereby reducing reactor fouling (see for example E. M. Carnahan, G. B. Jacobsen “Supported metallocene catalysts” CATTECH, in Kluwer Academic/Plenum Publishers, vol 4, n°1 , 74-88, 2000 ; G. Fink, B. Steinmetz, J. Zechlin, C. Przybyla,
• the heterogeneisation can optionaly be performed by the covalent anchorage of the metallocene complexes on mineral oxide supports as described for example in EP-A- 293815, or in US-A-5262498, or in US-A-5688880, or in US-A-5854362, or in US-A- 5399636 or in H. G. Alt, P. Schertl, A. Koppl, "Polymerization of ethylene with metallocene/methylaluminoxane catalysts supported on polysiloxane microgels and silica.” in J. Organometal. Chem., 568, 263-269, 1998, or in M. Galan-Fereres, T. Koch, E. Hey-Hawkins, M.S.
• the catalyst component can also be deposited on polymer supports as described for example in T. R. Boussie, C. Coutard, H. Turner, V. Murphy, T.S. Powers, "Solid- phase synthesis and encoding strategies for olefin polymerization catalyst libraries" in Angew. Chem. Int. Engl., 37, 3272-75, 1998 or in T.R. Boussie, V. Murphy, K.A. Hall,
• Another strategy concerns the covalent anchorage of dimethyanilinium cations on polymeric support which had to be achieved in order to allow immobilisation of the perfluorinated borate anions by ionic linkage as described in WO 98/55518 and in US-A-6228795.
• Kaneko and Sato (US-A-5807938) have anchored the p-trimethoxysily- (N,N-dimethylanilium) on a silica surface to afford an activated support for olefin polymerisation by addition of Li tetrakis(pentafluorophenyl)borate. They also claims the use of dimethyldimethoxysilane as co-grafting agent.
• metals can be selected from aluminium, titanium, zirconium or nickel.
• DMAF dimethylaluminium fluoride
• the present invention relates to :
• the present invention discloses a method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functional ised silylating agent of formula YsSi — L — NR' 2 wherein each R' is independently selected from alkyl, aryl, alkylaryl or arylalkyl, and a structurally similar non functionalised silylating agent Y 3 Si — L, said functional ised and non functionalised silylating agents being in a ratio ranging between 1 :1 and 1 :19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen and wherein L is a rigid linker group, preferably an aromatic group and more preferably a phenyl group
• step b) adding to the intermediate support of step b) a non-nucleophile trimethylsilylating agent selected from thmethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3- tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, thmethylsilyl-p-toluenesulfonate, hexamethyldisilazane, N,N-bis(trimethylsilyl) urea, N,O-bis(thmethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N- trimethylsilylthiazole, N-trimethylsilyloxazole or thalkylhalogens
• step d) protonating the intermediate amine-grafted supports of step c) with an acid AH in order to form the protonated intermediate supports
• A is triflate CF 3 SO 2 O (OTf) or halogen
• step d) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support S ac t
• the present invention discloses a method for preparing an activating support that comprises the steps of: a) providing a support prepared from silica or from mixed mineral oxides based on silica; b) grafting on the surface of the support of step a) a mixture of silylating agents comprising a functional ised silylating agent of formula YsSi — L — CH 2 — Z and a structurally similar non functionalised silylating agent Y 3 Si — L, said functionalised and non functionalised silylating agents being in a ratio ranging between 1 :1 and 1 :19 and wherein each Y is independently selected from alkoxy, halogen or hydrogen, L is a rigid linker group and Z is a leaving group, in order to prepare modified support
• step b) adding to the modified support of step b) a non-nucleophile trimethylsilylating agent selected from trimethylphenoxysilane, phenyldimethylphenoxysilane, hexamethyldisiloxane, 1 ,1 ,3,3-tetramethyldisiloxane, trimethylsilyl methanesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl-p- toluenesulfonate, hexamethyldisilazane, N,N-bis(thmethylsilyl) urea, N 1 O- bis(thmethylsilyl) acetamide, N-trimethylsilyl acetamide, N-methyl-N- trimethylsilyltrifluoroacetamide, N-trimethylsilylimidazole, N-trimethylsilylthiazole, N-trimethylsilyloxazole or trialkylhalogensilanes such
• step a) adding to the passivated support of step c) a secondary amine of formula
• R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group and Ar is substituted or unsubstituted aryl group, in order to provide intermediate support
• A is triflate CF 3 SO 2 O (OTf) or halogen; f) adding a borate or aluminate XM to the intermediate support of step d) wherein X is Al- or B-containing activating group and M is a metal Group 1 of the Periodic Table, in order to provide activating support S ac t
• the support is preferably selected from SiO 2 , SiO 2 / AI 2 O 3 , SiO 2 / TiO 2 , SiO 2 / ZrO 2 , SiO 2 / LnO x wherein Ln stands for lanthanides.
• R' is alkyl group having from 1 to 6 carbon atoms or aryl group. More preferably, R' is methyl, butyl or phenyl. Most preferably it is phenyl.
• At least one of R' and L must be aryl group.
• Leaving group Z is preferably selected from halogen, paratoluenesulfonate, triflate and diazonium.
• X is preferably selected from tetrakis-(pentafluoroaryl)borate or tetrakis- (pentafluoroaryl)aluminate.
• M is lithium.
• the support can also be modified in order to tailor its characteristics such as its specific surface area, its pore volume, its acidity or its hydrophobic or hydrophilic character.
• the method for preparing an activating support comprises the steps of: a) providing a support selected from Si ⁇ 2, SiO 2 / AI2O3, SiO 2 / TiO 2 , SiO 2 / ZrO 2 , SiO 2 / LnO x ; b) grafting on the surface of the support of step a) a mixture of para- aminophenylsilane and of phenylsilane chains in a ratio ranging from 1 :1 to 1 :19; c) N-alkylating the amino-groups of the support of step b) in order to prepare an intermediate support bearing grafted para- ⁇ /, ⁇ /-dialkyl-aminophenylsilane and phenylsilane in a ratio ranging from 1 :1 to 1 :19
• step c) adding to the intermediate support of step c) a trimethylsilylating agent such as for example trimethylsilylimidazole or hexamethyldisilazane
• a trimethylsilylating agent such as for example trimethylsilylimidazole or hexamethyldisilazane
• the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in starting silica-based support; e) prtonating the intermediate amine grafted support of step d) with an acid AH to
• A is Otf or halogen; f) adding a borate or aluminate XM to the intermediate supports of step e) wherein X is an activating group containing Al " or B " , and M is a metal Group 1 of the Periodic Table, in order to provide activating support
• the method for preparing an activating support comprises the steps of: a) providing a support selected from SiO 2 , SiO 2 / AI 2 O 3 , SiO 2 / TiO 2 , SiO 2 / ZrO 2 , SiO 2 / LnO x ; b) grafting on the surface of the support of step a) a functionalised silylating agent of formula (RO) 3 Si — Ar — CH 2 — X or a mixture of silylating agents comprising a functionalised silylating agent of formula (RO) 3 Si — Ar — CH 2 — X and a structurally similar non functionalised silylating agent (RO) 3 Si — Ar, being in a ratio ranging between 1 :1 and 1 :19 and wherein OR is an alkoxy group, Ar is an aromatic group, preferably a phenyl ring and X is an halogen, in order to prepare modified support
• step e) adding to the modified supports of step e) a non-nucleophile trimethylsilylating agent of formula
• step a) wherein the amount of trimethylsilylating agent is selected to provide at least 5 equivalents of silanol with respect to silanol present in the starting silica- based support of step a);
• R is alkyl group having from 1 to 6 carbon atoms or substituted or unsubstituted aryl group, preferably an alkyl group and Ar is an aromatic group in order to provide intermediate supports
• A is OTf or halogen
• step e) adding a borate or aluminate: XM to the intermediate supports of step e) wherein X is an activating group containing Al " or B " , and M is a metal Group 1 of the Periodic Table, in order to provide activating support
• the present invention also discloses the activating supports obtainable by the method of the present invention.
• metallocene or late transition metal complex catalyst components prepared by any method known in the art can be deposited on the activating support of the present invention in order to provide active catalyst systems without addition of conventional activating agents such as aluminoxanes or boron- based compounds.
• Preferred metallocene catalyst components according to the present invention include compounds based on bridged bisindenyl, bistetrahydroindenyl or cyclopentadienyl-fluorenyl ligands. The metallocene catalyst component must be fully alkylated.
• Late transition metal complexes of the present invention preferably include ⁇ -diimine Ni complexes as disclosed by Brookhart in WO96/ 23010 or bis(imino)pyridyl Iron(ll) or Cobalt(ll) complexes as disclosed by Bristovsek et al. (GJ. P.
• Late transition components must also be fully alkylated. If not an alkylating agent such as aluninium alkyl must be added in order alkylate the compound.
• the present invention thus discloses a method for preparing an active catalyst system by the steps of: a) providing an activating support as described hereabove; b) impregnating a fully alkylated metallocene or post-metallocene catalyst component onto the activating support; c) optionally adding a scavenger; d) retrieving an active catalyst system.
• the scavenger is an aluminium alkyl. It is preferably selected from thisobutyl aluminium (TIBAL), thethylaluminium (TEAL) or thmethylaluminium.
• the active catalyst systems of the present invention are used for the oligomerisation or the homo- or co-polymerisation of ethylene and alpha-olefins. They have the advantage of being very efficient without the need to add costly and dangerous material such as methylaluminoxane.
• the present invention thus discloses a method for oligomehsing or homo- or co- polymerising that comprises the steps of: a) injecting the active catalyst system of the present invention into the reactor; b) injecting the monomer and optional comonomer simultaneously with or after the catalyst system; c) optionally injecting a scavenger; d) maintaining under polymerization conditions; e) retrieving a polymer.
• the monomer is preferably ethylene or propylene.
• the comonomer is preferably ethylene, propylene or 1 -hexene.
• the starting silica support used in all examples was from Grace Davison (G5H, Surface area: 513 m 2 .g "1 ; porous volume : 1.8 mL.g "1 Supported ammonium.
• Example 1 preparation of sample (AEiP-A/B) or grafting para- aminophenylthmethoxysilane on silica.
• the first step was the anchoring of paraaminophenyltrimethoxysilane (4.43 g, 0.02 mol) on activated silica. It was carried out under toluene reflux (60 0 C for 6h and 120 0 C for 1 h) and the reaction was catalysed by a ternary system consisting of water (373 ⁇ l_), paratoluene sulfonic acid (195.88 mg) and ammonium fluoride
• the fourth step was the quaternisation of the resulting tertiary amines by protonation with trifluoromethane sulfonic acid.
• 300 mg of prepared material were activated under vacuum at room temperature for 2 hours.
• Toluene (8 ml_) was then added.
• the suspension was stirred for 10 mn and a solution of trifluoromethanesulfonic acid (150 ⁇ l_ diluted in 2 ml_ of toluene) was added.
• the mixture was stirred at room temperature for 24 hours.
• the solution was filtered, washed several times with toluene, and tetrahydrofurane (THF). The material was dried for 2 hours.
• the fifth step was the introduction of the borate group: it was carried out by exchange reaction with OSO 2 CF 3 (OTf) anion.
• Compound B(C 6 Fs) 4 Li was synthetised by reacting C 6 F 5 Li (138 ⁇ l_, 1.26 mmol) with B(C 6 Fs) 3 (0.65g, 1.26 mmol). It was then reacted with R 3 N + H, OTf to form R 3 N + H, B(C 6 F 5 ) 4 with release of LiOTf.
• the resulting material was analysed and had the following properties: SBET : 1 18 m 2 /g.
• ATG 1.93 % (H 2 O) ; 37.06 % (organic moieties) ; 60.59 % (SiO 2 ).
• Example 2 preparation of sample (AE?P-A/B) or grafting and dispersing para- aminophenyltrimethoxysilane on silica.
• AE2P-A/B preparation of sample (AE 3 P-AZB) or grafting and paramethylchlorophenylthmethoxysilane on silica.
• the silanols were passivated by reaction with N 1 O- bistrimethylsilyltrifluoroacetamide that was selected because it was not very nucleophile and thus not likely to initiate the substitution of chlorine.
• 5.75 g of the material prepared in the first step were heated at a temperature of 150°C for a period of time of 16h. 60 ml_ of toluene were then added. After stirring for 15 minutes, N, O- bis(trimethylsilyl)trifluoroacetamide (4.40 ml_) was introduced dropwise as silylating agent.
• N-methylaniline (5.4 ml_) was first synthetised. It was then mixed with thethylamine (5.4 ml_) and added to a suspension of activated chlorobenzene supported silica (5.44 g of activated support in 50 ml_ of toluene). The mixture was heated at a temperature of 80 0 C for a period of time of 36h. The nucleophilic reaction between secondary amine and chloride as leaving group resulted in the formation of the corresponding tertiary amine with elimination of HCI. The latter was then neutralised with thethylamine leading precipitation of chlorhydrate.
• the tertiary amines were quaternised by protonation with trifluoromethane sulfonic acid (HOTf).
• HATf trifluoromethane sulfonic acid
• the tertiary amino supported silica 1.5 g was activated under vacuum at room temperature for 3 hours and toluene (20 ml_) was then added.
• a solution of thfluoromethanesulfonic acid (0.45 ml_) in 5 ml_ of toluene was added dropwise. The mixture was stirred for 24 hours at room temperature.
• the solution was filtered and washed with toluene and tetrahydrofurane.
• the material was then dried under vacuum for 4 hours.
• Example 4 preparation of sample (AE 4 P-AZB) or grafting and dispersing paramethylchlorophenyltrimethoxysilane on silica.
• the activating supports of examples 1 to 4 were used to polymerise ethylene under the following conditions, using a metallocene complex: SPEC Solvent: 20 ml_ of heptane Scavenger: 1 ml_ of triisobutylaluminiunn (TIBAL)

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